CN116425691A - Preparation method of 5-aminotetrazole - Google Patents
Preparation method of 5-aminotetrazole Download PDFInfo
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- CN116425691A CN116425691A CN202310255778.6A CN202310255778A CN116425691A CN 116425691 A CN116425691 A CN 116425691A CN 202310255778 A CN202310255778 A CN 202310255778A CN 116425691 A CN116425691 A CN 116425691A
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- aminotetrazole
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- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 25
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000001816 cooling Methods 0.000 claims abstract description 19
- 239000000047 product Substances 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 50
- 238000006243 chemical reaction Methods 0.000 claims description 40
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 11
- 239000012065 filter cake Substances 0.000 claims description 11
- 239000012043 crude product Substances 0.000 claims description 10
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 9
- 235000010288 sodium nitrite Nutrition 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 20
- 238000001914 filtration Methods 0.000 abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 10
- 239000007864 aqueous solution Substances 0.000 abstract description 8
- 238000006193 diazotization reaction Methods 0.000 abstract description 6
- 239000012467 final product Substances 0.000 abstract description 4
- 238000007363 ring formation reaction Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 230000002378 acidificating effect Effects 0.000 abstract description 3
- 238000004128 high performance liquid chromatography Methods 0.000 abstract description 3
- 238000004811 liquid chromatography Methods 0.000 abstract description 3
- 150000007522 mineralic acids Chemical class 0.000 abstract description 3
- 238000005580 one pot reaction Methods 0.000 abstract description 3
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract description 2
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 150000001540 azides Chemical class 0.000 abstract 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 8
- 230000001276 controlling effect Effects 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 description 4
- HAMNKKUPIHEESI-UHFFFAOYSA-N aminoguanidine Chemical compound NNC(N)=N HAMNKKUPIHEESI-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- BIVUUOPIAYRCAP-UHFFFAOYSA-N aminoazanium;chloride Chemical compound Cl.NN BIVUUOPIAYRCAP-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000002360 explosive Substances 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- VTUFDOOSZOYXFC-UHFFFAOYSA-N 2-amino-1-(diaminomethylidene)guanidine Chemical compound NNC(=N)NC(N)=N VTUFDOOSZOYXFC-UHFFFAOYSA-N 0.000 description 2
- WTLKTXIHIHFSGU-UHFFFAOYSA-N 2-nitrosoguanidine Chemical compound NC(N)=NN=O WTLKTXIHIHFSGU-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- BNWPUUZJGBXAFM-UHFFFAOYSA-N azane oxalonitrile Chemical compound N.N#CC#N BNWPUUZJGBXAFM-UHFFFAOYSA-N 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- UBDZFAGVPPMTIT-UHFFFAOYSA-N 2-aminoguanidine;hydron;chloride Chemical compound [Cl-].NC(N)=N[NH3+] UBDZFAGVPPMTIT-UHFFFAOYSA-N 0.000 description 1
- CSPTZWQFHBVOLO-UHFFFAOYSA-N 4-phenyldiazenylbenzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1N=NC1=CC=CC=C1 CSPTZWQFHBVOLO-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000004204 blood vessel Anatomy 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- KCCKZVUDDJTOFK-UHFFFAOYSA-N hydrazine;hydrate;hydrochloride Chemical compound O.Cl.NN KCCKZVUDDJTOFK-UHFFFAOYSA-N 0.000 description 1
- JUINSXZKUKVTMD-UHFFFAOYSA-N hydrogen azide Chemical compound N=[N+]=[N-] JUINSXZKUKVTMD-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- WURGAKORBPRKIL-UHFFFAOYSA-N tetrazolidine-1,2,3,4,5-pentamine Chemical compound NC1N(N)N(N)N(N)N1N WURGAKORBPRKIL-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D257/00—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms
- C07D257/02—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D257/04—Five-membered rings
- C07D257/06—Five-membered rings with nitrogen atoms directly attached to the ring carbon atom
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of 5-aminotetrazole, which comprises the following steps: sequentially adding inorganic acid and cyanuric acid solution into hydrazine hydrate aqueous solution, then adding nitrite aqueous solution under the protection of nitrogen in an acidic environment for diazotization, then adding alkaline substances and active carbon for heating for cyclization, then filtering, adjusting pH to 3.5-4.1, cooling, filtering, crystallizing, and recrystallizing to obtain 5-aminotetrazole; the preparation process is simple, no azide acid is adopted, the environmental pollution is small, the final product can be obtained in one pot, the process steps are concise, the yield of the final obtained wide product can reach 86%, and the purity of the product can reach more than 98.5% as determined by liquid chromatography (HPLC).
Description
Technical Field
The invention belongs to the field of material chemistry, and in particular relates to a preparation method of a high-energy material raw material pentaamino tetrazole.
Background
In recent years, with the development of the automobile industry and the improvement of safety requirements, 5-aminotetrazole (CH 3 N 5 CAS 4418-61-5) has gradually replaced sodium azide (which is more toxic) as the primary gas generator for automotive airbags due to safer performance and no pollution. The conventional 5-aminotetrazole is a Stollet method and an aminoguanidine diazonium cyclization method which are directly synthesized by utilizing hydrazoic acid (sodium azide) and cyanmine (dicyandiamide), the method of one-pot method does not involve transfer of intermediate products, and the product color is white-like, the purity reaches 98 percent, and the yield is 75 percent. The former method is simple in process, but the raw material of the azoic acid is high-energy explosive, is extremely dangerous to use and store, and has damage to human blood vessels, so that the method is not suitable for large-scale industrial production. The latter process uses cyanoguanidine as a starting material which is also difficult to prepare and requires stringent storage and transportation conditions. These factors lead to high product cost, difficult three-waste treatment and limited industrial production, so a new technology is urgently needed to solve the existing problems so as to meet the market demand.
Disclosure of Invention
Aiming at the problems, the application provides a novel one-pot synthesis route of 5-aminotetrazole, and the final product can be prepared by recrystallization in the same container, so that intermediate products are not required to be separated and extracted, the operation is simple, the production cost is low, and the environmental pollution is small.
Specifically, the application is realized through the following technical routes:
a preparation method of 5-aminotetrazole comprises the following steps;
1) Adding hydrazine hydrate into a reaction kettle, cooling to 0-10 ℃, dropwise adding concentrated hydrochloric acid at the temperature of 0-20 ℃ and then adjusting the pH value to 6.5-6.9 to obtain hydrazine hydrate hydrochloride;
in the specific implementation, the pH of the reaction system can be adjusted to 6.5-6.9 by adding ammonia water (such as ammonia water with the mass concentration of 25 percent) or hydrochloric acid (such as 36 percent by mass);
wherein, the molar ratio of hydrazine hydrate to hydrochloric acid is preferably 1-1.1:1, a step of; the mass percentage of the added concentrated hydrochloric acid is preferably 30% -37%, and in one embodiment of the application, is preferably 36.5%.
2) Heating to 85deg.C, and adding Shan Qingan solution (H 2 NCN, also called cyanamide), controlling the temperature within the range of 85-95 ℃ in the dripping process, and reacting for 2-3 hours at the temperature of not lower than 75 ℃ after finishing dripping to generate aminoguanidine;
in the step, the reaction temperature after the dripping is completed cannot be lower than 75 ℃, preferably 85-95 ℃, so as to prevent the generation of urea as a byproduct;
the mass concentration of the aqueous cyanamide solution used is preferably 45-50%.
The molar ratio of the added cyanamide to the hydrazine hydrate is 1.3-1.1:1 (preferably the molar ratio is 1.18:1), and the reaction time is preferably 3 hours.
4) Dropwise adding concentrated hydrochloric acid (with the mass concentration of 30% -37%, preferably 36.5%) at the temperature of not more than 40 ℃ (preferably 0 ℃ -20 ℃);
the molar ratio of the hydrochloric acid added in the step to the hydrazine hydrate added in the step 1) is 1.0-2.0: 1, preferably 1.5:1.
dropwise adding a sodium nitrite solution into a reaction system at the temperature of 10-20 ℃ under the protection of nitrogen, and reacting for 20-60 minutes (preferably 30 minutes) after the dropwise adding is finished, so as to carry out diazotization reaction;
the sodium nitrite solution is prepared from sodium nitrite and deionized water according to a mass ratio of 1:3-6, mixing to obtain the product; the mass ratio of the sodium nitrite to the deionized water is preferably 1:3.
5) After the diazotization reaction of the step 4) is completed, adding ammonia water into a reaction system, adding active carbon, heating to 98-105 ℃, refluxing for 2-3 hours (preferably 2 hours), and carrying out cyclization reaction;
the mass concentration of the ammonia water used in the step is 20% -25% (preferably 25%), and the molar ratio of ammonia in the ammonia water to hydrazine hydrate added in the step 1) is 1.38-2.38: 1, preferably 1.88:1, a step of;
the mass ratio of the activated carbon added in the step to the hydrazine hydrate added in the step 1) is 100:1-3, preferably 100:1;
6) Step 5), after the reaction is finished, regulating the pH of a reaction system to 3.5-4.1 (the pH is preferably 4.0-4.1), crystallizing at 0-10 ℃, carrying out suction filtration, taking a filter cake, rinsing with deionized water, and baking at 80-110 ℃ to constant weight to obtain a pure white solid, namely a 5-aminotetrazole crude product;
the pH of the reaction system is adjusted to 3.5-4.1 by concentrated hydrochloric acid (the mass concentration is 30-37%, preferably 36.5%);
7) Adding deionized water into the 5-aminotetrazole crude product obtained in the step 6), heating (for example, 100 ℃) until the solid is dissolved, then cooling to 0-10 ℃, carrying out suction filtration, taking a filter cake, and drying at 80-110 ℃ to obtain the 5-aminotetrazole;
in this step, deionized water is added in an amount of 2 to 3 times (preferably 3 times) the mass of the product 5-aminotetrazole (in 100% yield).
The chemical equation involved in the above reaction is as follows:
N 2 H 4 ·H 2 O+HCL→N 2 H 4 ·HCl
the reaction principle of the application is as follows: in step 1): firstly, hydrazine hydrate reacts with hydrochloric acid to form hydrazine hydrochloride mono-salt, hydrazine hydrochloride bi-salt does not react with the cyanamide in the step 2), and the hydrazine hydrate reacts with the cyanamide in the step 2) to form amino biguanide; then in step 2) hydrazine hydrate is reacted with hydrochloric acid to form aminoguanidine hydrochloride, which can undergo side reactions to form urea at temperatures below 75 ℃ (thus the reaction temperature is preferably 85 ℃ to 95 ℃); in the step 4), aminoguanidine is subjected to diazotization reaction under an acidic condition to generate azidocarbonxamidine, so that air is isolated to prevent nitrous acid from being oxidized by oxygen in the air to generate nitrosoguanidine; finally, in the 5) azidocarbonxamidine is cyclized under the weak acid condition to generate the target product 5-aminotetrazole.
The 5-aminotetrazole can be used as an intermediate of a propellant, an explosive, an initiating explosive, a medicine and a herbicide, a high-energy material raw material and a gas producer of an automobile safety airbag, and is suitable for industrial production.
Compared with the existing preparation method of the 5-aminotetrazole, the reaction route has the following beneficial effects:
(1) The synthetic route of the application is to add inorganic acid into hydrazine hydrate aqueous solution to make the hydrazine hydrate aqueous solution become hydrazine hydrate salt; then adding a cyanogen ammonia water solution to react to generate aminoguanidine salt; adding inorganic acid to provide an acidic environment, adding nitrite aqueous solution under the protection of nitrogen to carry out diazotization reaction, adding alkaline substances and active carbon to the reaction liquid after diazotization to regulate the pH value to 4-6, heating to carry out cyclization reaction, filtering the active carbon after reaction to regulate the pH value to 3.5-4.1, cooling, filtering, washing out separated pure white crystals, and recrystallizing the pure white crystals with purified water to obtain the 5-aminotetrazole.
(2) In the reaction route step 1), the amount of hydrochloric acid is strictly controlled, so that hydrazine hydrate and hydrochloric acid are formed, hydrazine hydrochloride is monohydrochloride, the generation of amino biguanide by side reaction is completely avoided, and the color of the product is pure white (only the color observation purity is higher).
(3) When the sodium nitrite aqueous solution is dripped in the step 4) of the reaction route, nitrogen is used for protection, so that the generation of nitrosoguanidine by side reaction is avoided, and the yield is further improved.
Drawings
FIG. 1 is a high performance liquid chromatogram of the sample obtained in example 1.
FIG. 2 shows a nuclear magnetic resonance spectrum of the sample obtained in example 1, in which the abscissa indicates the frequency HZ and the ordinate indicates the chemical shift pm.
FIG. 3 is a high performance liquid chromatogram of the sample obtained in example 2.
FIG. 4 is a high performance liquid chromatogram of the sample obtained in example 2.
FIG. 5 is a HPLC chromatogram of a control purchased from Shanghai microphone Biochemical technologies Co., ltd.
Detailed Description
Unless otherwise indicated, the raw materials and reagents used in the following examples were all commercially available.
Raw material hydrazine hydrate (N) used in examples 2 H 4 ·H 2 O, 80% by mass concentration), hydrochloric acid (36.5% by mass concentration), mono-cyanogen ammonia water solution (50% by mass concentration), sodium nitrite and ammonia water (25% by mass concentration) are all purchased from Shanghai Bi to medical science and technology Co.
Model and analysis conditions of the high performance liquid phase instrument: agilent model: agilent 1100;
the analysis method comprises the following steps: the volume ratio of potassium dihydrogen phosphate to acetonitrile is 95:5, the wavelength is 215nm, the flow is 0.8mL/min, the sample injection amount is 2 mu L, the column temperature is 40 ℃, the pressure is limited to 30Mpa, and the sample is 0.08g dissolved in acetonitrile in a 50mL volumetric flask.
The type of the magnetic resonance instrument and the analysis conditions are Bruker Avance DMX and 500 superconducting nuclear magnetism is adopted;
resonance spectrometer, resonance frequency is 400MHZ; with CDCl 3 、CD 2 Cl 2 、DMSO-D 6 As solvent, TMS as internal standard.
Example 1
1) Will N 2 H 4 ·H 2 O aqueous solution (12.5 g,1.0eq, mass fraction 80%) is added into a 250mL three-mouth bottle, the temperature is reduced to 0 ℃, HCl solution (21.95 g,1.1eq, mass fraction 36.5%) is added dropwise, the dropwise adding process is exothermic reaction, the temperature is controlled between 0 ℃ and 20 ℃, and the whole dropwise adding process lasts for 30min; then ammonia water with the mass concentration of 25% or concentrated hydrochloric acid with the mass concentration of 36.5 is added to reversely adjust the pH value of the reaction system to 6.7.
In the specific implementation, the pH of the reaction system is regulated to be in the range of 6.5-6.9 in the step, so that the aim of the invention can be fulfilled.
2) After the dripping is finished, the temperature is raised to 85 ℃, and H is dripped 2 NCN aqueous solution (19.82 g,1.18eq with hydrazine hydrate mol ratio, mass concentration 50%) for 30min, controlling the temperature of the reaction system in the range of 85-95 ℃ in the dropping process; after the dripping is finished, controlling the temperature within the range of 85-95 ℃ and reacting for 3 hours;
3) Cooling to 10deg.C, adding HCl (29.93 g,1.5eq, 36.5% hydrochloric acid solution) dropwise, and adding for 30min; then cooling to 17 ℃, replacing nitrogen for 3 times, and dripping NaNO 2 The solution is used for 40min, and the temperature is controlled between 17 ℃ and 22 ℃ in the dripping process; after the dripping is completedStirring and reacting for 30 minutes at 17-22 ℃ under the control of temperature, and removing nitrogen protection;
NaNO used in this step 2 The solution was prepared from 13.92g (1.0 eq) NaNO 2 A solution obtained after mixing with 45mL of deionized water (3V);
4) NH is added into the reaction system 3 (25.60 g,1.88eq, 25% by mass) and then adding activated carbon to adsorb colored macromolecular impurities (0.3 g,3% by mass of pure hydrazine hydrate), heating to 100 ℃ and refluxing, and treating for 2 hours.
Then cooling to 70 ℃, and adjusting the pH of the reaction solution to 4.0 by using HCL (10 g,0.4eq, mass fraction 36.5 percent); cooling to 10 ℃, stirring for 2 hours, crystallizing the reaction liquid, and filtering. And (3) rinsing the filter cake by using deionized ice water at the temperature of 0 ℃, and baking the filter cake to constant weight at the temperature of 80 ℃ to obtain pure white solid (namely the crude product of the 5-aminotetrazole).
In this step, the pH of the reaction solution is adjusted to 3.5-4.1, thereby achieving the object of the invention.
5) Adding ionized water (51 g,3 times of the 100% yield quality of the target product) into the 5-aminotetrazole crude product obtained in the step 4), heating to 100 ℃ to melt, stirring for 15min after melting, cooling to 5 ℃, filtering, taking a filter cake, and baking to constant weight at 80 ℃ to obtain 14.62g of white solid, namely the target product 5-aminotetrazole, wherein the yield is calculated to be 86.0% purity: 98.58%.
The liquid chromatogram of the final product 5-aminotetrazole obtained in this example is shown in FIG. 1, the nuclear magnetic resonance (HNMR) is shown in FIG. 2, DMSO is used as a solvent, and FIG. 5 is an HPLC chromatogram of a commercially available 5-aminotetrazole sample, which proves that the final product obtained in this example is 5-aminotetrazole.
Example 2
1) Will N 2 H 4 ·H 2 O (2.5 Kg,1.0eq, mass fraction 80%) was added to a 50L glass reactor, the reactor was cooled to 0℃and HCl (4.39 Kg,1.1eq, mass fraction 36.5%) was added dropwise over a period of 1h, followed by adjusting the pH of the reaction system to 6.7.
2) Heating to 85deg.C, and dripping Shan Qingan H at 85-95deg.C 2 NCN (3.96 Kg,1.18eq, mass fraction 50%), was added dropwise and reacted at 85-95℃for 3 hours.
3) Cooling to 0 ℃, dropwise adding HCl (6.07 Kg,1.5eq, mass fraction 36.5%), wherein the dropwise adding process temperature is in the range of 0-20 ℃.
4) Cooling to 17 ℃, introducing nitrogen into the reaction system for 3 times, and dropwise adding NaNO 2 Controlling the temperature of the solution in the dropping process within the range of 17-22 ℃; after the dripping is finished, stirring for 30 minutes, and removing the nitrogen protection;
in this step, naNO 2 The solution was prepared by mixing 2.76Kg (1.0 eq) NaNO 2 The resulting solution was dissolved in 6L (3V) deionized water.
5) Adding ammonia (NH) 3 ) (5.12 Kg,1.88eq, mass fraction 25%), activated carbon (60 g,3% of pure hydrazine mass) was added, reflux was heated to 100℃and reacted for 2 hours, filtration was carried out, and the filtrate was adjusted to pH 4.0 with HCL (1.60 Kg,0.4eq, mass fraction 36.5%) at 70 ℃.
Then cooling to 10 ℃, stirring for 2 hours, filtering, and rinsing the filter cake with deionized ice water at 0 ℃. And drying at 80 ℃ to constant weight to obtain an off-white solid, namely the crude product of the 5-aminotetrazole.
6) Adding ionized water (10.20 Kg,3 times of 100% yield quality of the target product) into the 5-aminotetrazole crude product obtained in the step 5), heating to 100 ℃ to melt, stirring for 15min after melting, cooling to 5 ℃, crystallizing and filtering, and drying a filter cake to constant weight of 2.94Kg at 80 ℃ to obtain the target product, namely the 5-aminotetrazole.
The yield of the target product of this example was 86.5% and the purity: 98.72% and its liquid chromatogram is shown in figure 3.
Example 3
1) Hydrazine hydrate N 2 H 4 ·H 2 O (165 Kg,1.0eq, mass fraction 80%) is added into a 1000L reaction kettle, the temperature is reduced to 0 ℃, HCl (289 Kg,1.1eq, mass fraction 36.5%) is added dropwise, and the temperature is controlled within the range of 0-20 ℃ in a dropwise manner; then adjusting the pH of the reaction system to 6.7;
2) Heating to 85deg.C, and dripping Shan Qingan H 2 NCN (262 Kg,1.18eq, mass fraction 50%), the temperature is controlled between 85 and 95 ℃ during the dripping period; after the dripping is finished, controlling the temperature to be between 85 and 95 ℃ for reaction for 3 hours.
3) Cooling to 0 ℃, dropwise adding HCl (395 Kg,1.5eq, mass fraction 36.5%), and controlling the temperature at 0-20 ℃ during the dropwise adding period;
4) Introducing nitrogen into the reaction system for 3 times, cooling to 17 ℃, and dripping NaNO 2 Controlling the temperature of the solution to be 17-22 ℃ during the dripping period; stirring for 30 minutes, and removing the nitrogen protection.
NaNO used in this step 2 The solution was 182Kg (1.0 eq) NaNO 2 The solution obtained was mixed with 396Kg (3V) deionized water.
5) Ammonia water (338 kg,1.88eq, 25% of ammonia mass) is added, activated carbon (3.69 kg, 3%) is added, the temperature is raised to 100 ℃ to reflux, activated carbon is removed by suction filtration for 2 hours, and HCL (105 kg,0.4eq, 36.5% of 3 mass fraction) is added to the filtrate at 70 ℃ to adjust the pH of the reaction solution to 4.0; then cooling to 0 ℃, stirring for 2 hours, crystallizing, soaking and washing a filter cake with deionized water (132 Kg,1 time of the mass of pure hydrazine hydrate) to obtain pure white solid, and drying to constant weight at 80 ℃ to obtain a 5-aminotetrazole crude product.
6) Adding deionized water (673 Kg,3 times of 100% yield quality of the product) into the 5-aminotetrazole crude product obtained in the step 5), heating to 100 ℃ to melt, stirring for 15min after melting, cooling to 5 ℃, crystallizing, filtering, and baking the filter cake to constant weight at 80 ℃ to obtain 195Kg of white solid, namely the target product 5-aminotetrazole.
The yield of the target product is calculated to be 87.0%, the purity of the target product is detected to be 99.71% by liquid chromatography, and the liquid chromatography is shown in figure 4.
While the foregoing is directed to embodiments of the present invention, other and further details of the invention may be had by the present invention, it should be understood that the foregoing description is merely illustrative of the present invention and that no limitations are intended to the scope of the invention, except insofar as modifications, equivalents, improvements or modifications are within the spirit and principles of the invention.
Claims (9)
1. The preparation method of the 5-aminotetrazole is characterized by comprising the following specific steps:
1) Dropwise adding a hydrochloric acid solution I into hydrazine hydrate at the temperature of 0-10 ℃, and then adjusting the pH value to 6.5-6.9; the molar ratio of the added hydrazine hydrate to the hydrochloric acid is 1-1.1:1, a step of;
2) Heating to 85 ℃, dropwise adding a cyanamide solution into the reaction system, and reacting for 2-3 hours at the temperature of not lower than 75 ℃ after the dropwise adding is finished; the molar ratio of the added cyanamide to the hydrazine hydrate is 1.3-1.1: 1, a step of;
3) Dropwise adding a hydrochloric acid solution II into the reaction system at the temperature of not more than 40 ℃; the molar ratio of the added hydrochloric acid to the hydrazine hydrate added in the step 1) is 1.0-2.0: 1, a step of;
4) Dropwise adding a sodium nitrite solution into the reaction system at the temperature of 10-20 ℃ in a nitrogen atmosphere, and reacting for 20-60 minutes after the dropwise adding is finished; the sodium nitrite solution is prepared from sodium nitrite and deionized water according to a mass ratio of 1:3-6, mixing to obtain the product;
sequentially adding ammonia water and active carbon into the reaction system, heating to 98-105 ℃, and carrying out reflux reaction for 2-3 hours; the molar ratio of ammonia in the ammonia water to hydrazine hydrate in the step 1) is 1.38-2.38: 1, a step of;
adjusting the pH of the reaction system to 3.5-4.1, cooling to 0-10 ℃, crystallizing the solution, carrying out suction filtration, taking a filter cake, washing with deionized water, and drying at 80-110 ℃ to constant weight to obtain a 5-aminotetrazole crude product;
adding deionized water into the 5-aminotetrazole crude product obtained in the step 6), heating to dissolve the solid, cooling to 0-10 ℃, carrying out suction filtration, taking a filter cake, and drying at 80-110 ℃ to obtain the 5-aminotetrazole.
2. The preparation method of 5-aminotetrazole according to claim 1, wherein the mass concentration of the hydrochloric acid solution I in the step 1) is 30% -37%; and 3) the mass concentration of the hydrochloric acid solution II is 30% -37%.
3. The preparation method of 5-aminotetrazole according to claim 1, wherein the mass concentration of the cyanamide solution in the step 2) is 45% -50%.
4. The method for preparing 5-aminotetrazole according to claim 1, wherein in the step 2), the step of dropwise adding the cyanamide into the reaction system is performed at 85-95 ℃.
5. The method for preparing 5-aminotetrazole according to claim 1, wherein the condition of not more than 40 ℃ in the step 3) means that the temperature is in the range of 0 ℃ to 20 ℃.
6. The preparation method of 5-aminotetrazole according to claim 1, wherein the mass concentration of the ammonia water in the step 5) is 20% -25%.
7. The method for preparing 5-aminotetrazole according to claim 1, wherein the mass ratio of the activated carbon added in the step 5) to the hydrazine hydrate added in the step 1) is 100:1-3.
8. The method for preparing 5-aminotetrazole according to claim 1, wherein the step 6) of adjusting the pH of the reaction system to 3.5-4.1 means adjusting the pH of the reaction system to 3.5-4.1 with 30% -37% by mass concentration of hydrochloric acid.
9. The method for preparing 5-aminotetrazole according to claim 8, wherein the step 6) of adjusting the pH of the reaction system to 3.5 to 4.1 means adjusting the pH of the reaction system to 4.0 to 4.1.
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